Bisazo dyes containing a 2-amino-substituted thiazole radical

ABSTRACT

Compounds of the general formula I ##STR1## where D is the radical of a diazo component, 
     R is hydrogen, hydroxy or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aralkyl, phenyl or heterocyclic ring, 
     R 1  and R 2  independently of one another are hydrogen or unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or aryl, or 
     R 1  and R 2  together with the nitrogen are a saturated heterocyclic 5-membered to 7-membered ring, 
     X is hydrogen, chlorine, bromine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, allyloxy, β-cyanoethoxy, benzyloxy, phenoxy, β-alkoxycarbonylethoxy, where alkoxy is of 1 to 4 carbon atoms, alkylmercapto of 1 to 4 carbon atoms, phenylmercapto or alkanoylamino of 1 to 4 carbon atoms, and 
     Y is chlorine, alkyl of 1 to 4 carbon atoms, allyloxy, alkoxy of 1 to 4 carbon atoms or β-cyanoethoxy, or 
     X and Y together are a fused benzene ring which is unsubstituted or substituted by alkyl, alkoxy, chlorine or bromine. 
     The compounds are in particular suitable for dyeing cotton and union fabrics of cotton and synthetic fibers, preferably polyesters. The dyeings obtained are, in part, very fast.

BACKGROUND OF THE INVENTION Summary of the Invention

The present invention relates to a compound of the general formula I##STR2## where

D is the radical of a diazo component,

R is hydrogen, hydroxy or unsubstituted or substituted alkyl, alkenyl,cycloalkyl, aralkyl, phenyl or heterocyclic ring,

R¹ and R² independently of one another are hydrogen or unsubstituted orsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or aryl, or

R¹ and R² together with the nitrogen are a saturated heterocyclic5-membered to 7-membered ring, and

X is hydrogen, chlorine, bromine, alkyl of 1 to 4 carbon atoms, alkoxyof 1 to 4 carbon atoms, allyloxy, β-cyanoethoxy, benzyloxy, phenoxy,β-alkoxycarbonylethoxy, where alkoxy is of 1 to 4 carbon atoms,alkylmercapto of 1 to 4 carbon atoms, phenylmercapto or alkanoylamino of1 to 4 carbon atoms and

Y is chlorine, alkyl of 1 to 4 carbon atoms, allyloxy, alkoxy of 1 to 4carbon atoms or β-cyanoethoxy, or

X and Y together are a fused benzene ring, the naphthalene nucleusformed being unsubstituted or substituted by alkyl, alkoxy, chlorine orbromine

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Specific examples of radicals X and Y, in addition to those alreadymentioned in giving the general definition, are:

CH₃, C₂ H₅, C₃ H₇, C₄ H₉, OCH₃, OC₂ H₅, OC₃ H₇, OC₄ H₉, H₃ COOCC₂ H₄ O,H₅ C₂ OOCC₂ H₄ O, H₇ C₃ OOCC₂ H₄ O, H₉ C₄ OOCC₂ H₄ O, H₃ CCONH, H₅ C₂CONH, CH₃ S, H₅ C₂ S, H₇ C₃ S and H₉ C₄ S.

Examples of radicals R, in addition to hydrogen and hydroxyl, are alkylor alkenyl of 1 to 5 carbon atoms which is unsubstituted or substitutedby hydroxyl, chlorine, cyano, alkoxy of 1 to 4 carbon atoms, alkanoyloxyof 1 to 4 carbon atoms, alkanoyl of 1 to 4 carbon atoms, alkoxycarbonyl(where alkoxy is of 1 to 4 carbon atoms), alkylmercapto of 1 to 4 carbonatoms, phenylmercapto, carbamoyl (which is unsubstituted or substituted)or sulfamoyl; cyclohexyl; phenylalkyl, where alkyl is of 1 to 5 carbonatoms; phenyl which is unsubstituted, or is monosubstituted orpolysubstituted by chlorine, bromine, hydroxyl, alkoxy of 1 to 4 carbonatoms, alkyl of 1 to 4 carbon atoms, phenyl, phenoxy, alkylmercapto of 1to 4 carbon atoms, phenylmercapto, alkanoylamino of 1 to 5 carbon atoms,β-cyanoethoxy, β-alkoxyethoxy (where alkoxy is of 1 to 4 carbon atoms),β-alkoxycarbonylethoxy (where alkoxy is of 1 to 4 carbon atoms),β-cyanoethylmercapto, β-alkoxyethylmercapto (where alkoxy is of 1 to 4carbon atoms) or β-alkoxycarbonylethylmercapto (where alkoxy is of 1 to4 carbon atoms); furyl, pyridyl or thienyl.

Specific examples of radicals R, in addition to those already mentioned,are:

C₆ H₃ (CH₃)₂, C₆ H₄ CH₃, C₆ H₄ C₂ H₅, C₆ H₄ Cl, C₆ H₃ Cl₂, C₆ H₄ Br, C₆H₃ Br₂, C₆ H₄ F, C₆ H₃ F₂, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₅, C₆ H₄ OC₂ H₄ CN, C₆H₄ OC₂ H₄ COOCH₃, C₆ H₄ OC₂ H₄ COOC₂ H₅, C₆ H₄ OC₆ H₅, C₆ H₄ NHCOCH₃, C₆H₄ NHCOC₂ H₅, C₆ H₄ NH₂, C₆ H₄ NHCH₃, ##STR3## C₆ H₄ SCH₃, C₆ H₄ SC₆ H₅,CH₃, C₂ H₅, ClCH₂, C₂ H₅ OOC--CH₂, CH₃ OOC--CH₂ and NC--CH₂.

The radicals R¹ and R², which may be identical or different, arehydrogen or, for example, alkyl of 1 to 8 carbon atoms which isunsubstituted, alkyl of 2 to 8 carbon atoms which is substituted byhydroxyl, cyano, alkoxycarbonyl (where alkoxy is of 1 to 8 carbonatoms), alkoxy of 1 to 8 carbon atoms, phenoxy, phenoxyethoxy orbenzyloxy, cyclohexyl, benzyl, phenylethyl, phenylhydroxyethyl,phenylpropyl, phenylbutyl, phenyl, which is unsubstituted or substitutedby chlorine, methyl, methoxy or ethoxy, polyalkoxyalkyl,hydroxypolyalkoxyalkyl, alkanoyloxyalkyl or alkoxycarbonylalkyl of thetype mentioned below.

Specific examples of radicals R¹ and R² are, amongst alkyl radicals,methyl, ethyl, propyl and butyl; amongst hydroxyalkyl radicals,β-hydroxyethyl, β-hydroxypropyl, γ-hydroxypropyl and ω-hydroxyhexyl;β-alkoxycarbonylethyl (where alkoxy is of 1 to 4 carbon atoms) and theradicals of the formulae ##STR4## and the acyloxyalkyl radicals of theformulae ##STR5## where acyl may be, for example, --COH, --COCH₃,--COCH₂ --O--C₆ H₅, or COOB or CONHB, where B is methyl or phenyl.

R¹ and R² may also be components of a heterocyclic ring, for example##STR6##

The radical D of the diazo component is most frequently derived from theaniline, naphthalene, thiophen, aminoazobenzene, thiazole orbenzthiazole series.

Examples of substituents of the radicals D of the diazo component are:

In the benzene series: chlorine, bromine, nitro, cyano, trifluoromethyl,methylsulfonyl, ethylsulfonyl, phenylsulfonyl, carbomethoxy,carbobutoxy, carbo-β-methoxyethoxy, carboxamide and sulfonamide, whichare unsubstituted or N-monosubstituted or N-disubstituted, methyl,ethyl, methoxy and ethoxy. In this context, examples of N-substituentsof carboxamide or sulfonamide groups are methyl, ethyl, propyl, butyl,β-ethylhexyl, β-methoxyethyl, γ-methoxypropyl and γ-ethoxypropyl; theamide portion of a substituted carboxamide or sulfonamide may also bepyrrolidide, piperidide or morpholide.

In the azobenzene series: chlorine, bromine, nitro, cyano, methyl,hydroxyl, ethyl, methoxy and ethoxy.

In the heterocyclic series: chlorine, bromine, nitro, cyano, methyl,ethyl, phenyl, methoxy, ethoxy, carbomethoxy, carboethoxy, acetyl,methylsulfonyl and ethylsulfonyl.

Specific examples of amines from which the radical D may be derived are:aniline, o-, m- and p-toluidine, o-, m- and p-nitroaniline, o-, m- andp-cyanoaniline, 2,4-dicyanoaniline, o-, m- and p-chloroaniline, o-, m-and p-bromoaniline, 2,4,6-tribromoaniline, 2-chloro-4-nitroaniline,2-bromo-4-nitroaniline, 2-cyano-4-nitroaniline,2-methylsulfonyl-4-nitroaniline, 2-methyl-4-nitroaniline,2-methoxy-4-nitroaniline, 4-chloro-2-nitroaniline,4-methyl-2-nitroaniline, 4-methoxy-2-nitroaniline,1-amino-2-trifluoromethyl-4-chlorobenzene, 2-chloro-5-aminobenzonitrile,2-amino-5-chlorobenzonitrile, 1-amino-2-nitrobenzene-4-sulfonic acidn-butylamide and β-methoxyethylamide, 2,4-dinitroaniline,2,4-dinitro-6-chloroaniline, 2,4-dinitro-6-bromoaniline,2,4-dinitro-6-cyanoaniline, 1-amino-2,4-dinitrobenzene-6-methylsulfone,2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitroaniline,2-chloro-6-bromo-4-nitroaniline, 2,6-dicyano-4-nitroaniline,2-cyano-4-nitro-6-chloroaniline, 2-cyano-4-nitro-6-bromoaniline,1-aminobenzene-4-methylsulfone,1-amino-2,6-dibromo-benzene-4-methylsulfone,1-amino-2,6-dichlorobenzene-4-methylsulfone,1-amino-2,4-dinitrobenzene-6-carboxylic acid methyl ester andβ-methoxyethyl ester, propyl 3,5-dichloroanthranilate, β-methoxyethyl3,5-dibromoanthranilate, N-acetyl-p-phenylenediamine,4-aminoacetophenone, 4- and 2-amino-benzophenone, 2- and4-aminodiphenylsulfone, methyl, ethyl, propyl, butyl, isobutyl,β-methoxyethyl and β-ethoxyethyl 2-aminobenzoate, 3-aminobenzoate and4-aminobenzoate, methyl, isobutyl, β-methoxyethyl and β-butoxyethyl5-nitro-anthranilate, 3- and 4-aminobenzoic acid amide, methylamide,propylamide, butylamide, isobutylamide, cyclohexylamide,β-ethyl-hexylamide, γ-methoxypropylamide and γ-ethoxypropylamide, 2-, 3-and 4-aminobenzoic acid dimethylamide, diethylamide, pyrrolidide andmorpholide, 2-, 3- and 4-aminobenzenesulfonic acid dimethylamide anddiethylamide and 2-aminobenzthiazole.

Examples of suitable diazo components of the aminoazobenzene series are:4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene,3',2-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene,2-methyl-5-methoxy-4-aminoazobenzene,2-methyl-4',5-dimethoxy-4-aminoazobenzene,2,5-dimethoxy-4-aminoazobenzene,4'-methoxy-2,5-dimethyl-4-aminoazobenzene and3-methoxy-4-aminoazobenzene.

The diazo components preferably have, for example, the followingformulae: ##STR7##

A compound of the formula I may be prepared by reacting a diazoniumcompound of an amine of the formula ##STR8## with a coupling componentof the formula II ##STR9## D, X, Y, R, R¹ and R² having the meaningsgiven above.

Details of the method of preparation may be found in the Examples, whereparts and percentages are by weight, unless stated otherwise.

Compounds of the formula II may be prepared by a method similar to thatdescribed in French Pat. No. 1,600,940.

In particular, the invention provides compounds of the formula I, where

D is phenyl which is substituted by fluorine, chlorine, bromine, nitro,phenylazo, cyano, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 4 carbonatoms, alkoxycarbonyl (where alkoxy is of 1 to 8 carbon atoms),alkylsulfonyl of 1 to 4 carbon atoms, ##STR10## or trifluoromethyl, oris thiazolyl which is unsubstituted or substituted by methyl, nitro,alkanoyl of 1 to 4 carbon atoms, alkoxycarbonyl (where alkoxy is of 1 to5 carbon atoms), cyano, carbamoyl or phenyl, or is benzthiazolyl whichis unsubstituted or substituted by chlorine, bromine, alkoxy of 1 to 4carbon atoms, nitro, alkoxycarbonyl (where alkoxy is of 1 to 4 carbonatoms) or methyl-sulfonyl or is 1,2-benzisothiazolyl or2,1-benzisothiazolyl, which are unsubstituted or substituted bychlorine, bromine, nitro or cyano, R is phenyl which is unsubstituted oris monosubstituted or polysubstituted by chlorine, bromine, hydroxyl,alkoxy of 1 to 4 carbon atoms, phenoxy, alkyl of 1 to 10 carbon atoms,phenyl, alkylmercapto of 1 to 4 carbon atoms, phenylmercapto,alkanoylamino of 1 to 8 carbon atoms, β-cyanoethoxy, β-alkoxyethoxy(where alkoxy is of 1 to 4 carbon atoms), β-alkoxycarbonylethoxy (wherealkoxy is of 1 to 4 carbon atoms), β-cyanoethylmercapto, β-alkoxyethylmercapto (where alkoxy is of 1 to 4 carbon atoms) orβ-alkoxycarbonylethylmercapto (where alkoxy is of 1 to 4 carbon atoms),or is naphthyl, pyridyl, furyl or thienyl.

R¹ and R² independently of one another are hydrogen or allyl or arealkyl of 1 to 8 carbon atoms which is unsubstituted or substituted bycyano, alkoxycarbonyl (where alkoxy is of 1 to 8 carbon atoms), (OCH₂CH₂)_(n) OT, ##STR11## or phenyl, or are cyclohexyl orphenylhydroxyethyl, or are phenyl which is unsubstituted or substitutedby chlorine, methyl, methoxy or ethoxy, or

R¹ and R² together with the nitrogen are pyrrolidino, piperidino,morpholino, hexamethyleneimino or N-methylpiperazino,

n is 0, 1 or 2,

T is hydrogen, alkyl of 1 to 8 carbon atoms, cyclohexyl, benzyl,phenylethyl, phenyl, tolyl or alkanoyl of 1 to 8 carbon atoms, and

X is hydrogen, chlorine, bromine, alkyl of 1 to 4 carbon atoms, alkoxyof 1 to 4 carbon atoms, allyloxy, β-cyanoethoxy, benzyloxy, phenoxy,β-alkoxycarbonylethoxy (where alkoxy is of 1 to 4 carbon atoms),alkylmercapto of 1 to 4 carbon atoms, phenylmercapto or alkanoylamino of1 to 4 carbon atoms, and

Y is chlorine, alkyl of 1 to 4 carbon atoms, allyloxy, alkoxy of 1 to 4carbon atoms or β-cyanoethoxy, or

X and Y together are a fused benzene ring, the naphthalene nucleusformed being unsubstituted or substituted by alkyl of 1 to 4 carbonatoms, chlorine or bromine.

Compounds of particular industrial importance are those of the formulaIa ##STR12## where

B is

C₆ H₅, C₆ H₄ CH₃, C₆ H₄ C₂ H₅, C₆ H₄ Cl, C₆ H₃ Cl₂, C₆ H₄ OCH₃, C₆ H₄OC₂ H₄ CN, C₅ H₄ NHCOCH₃ or C₆ H₄ NH₂,

B¹ and B² independently of one another are

CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₂ H₄ COOCH₃, C₂ H₄ COOC₂ H₅, C₂ H₄ CN, C₂ H₄OH, C₂ H₄ C₆ H₅, C₂ H₄ OCOCH₃, C₂ H₄ OC₂ H₄ OC₆ H₅, C₂ H₄ OCH₃, C₃ H₆OCH₃, C₆ H₅, C₆ H₄ Cl, benzyl or CH₂ CH═CH₂,

X¹ is OCH₃, OC₂ H₅, OC₄ H₉, OC₂ H₄ CN, OC₂ H₄ COOCH₃, CH₃, C₂ H₅, SCH₃,NHCOCH₃ or NHCOC₂ H₅ and

Y¹ is OCH₃, OC₂ H₅, OC₄ H₉, OC₂ H₄ CN, CH₃ or C₂ H₅ and X¹ and Y¹ may beidentical or different,

Z¹ is hydrogen, chlorine, bromine, cyano or nitro,

Z² is hydrogen, chlorine, bromine or nitro and

Z³ is hydrogen, chlorine, bromine, cyano or alkoxycarbonyl (where alkoxyis of 1 to 4 carbon atoms).

The dyes of the formula I are preferentially usable for dyeing and, inparticular, printing cotton and union fabrics containing cotton, theother component preferably being a polyester. Suitable dyeing andprinting processes are those described in German Pat. No. 1,811,796. Thedyes of the invention, which have a high tinctorial strength, givelightfast and wetfast dyeings and prints which also have good fastnessto crocking.

EXAMPLE 1

17.2 parts of 2-chloro-4-nitroaniline are diazotized in the conventionalmanner. A solution of 15.3 parts of 1-amino-2,5-dimethoxybenzene in 300parts of water and 25 parts of 5-normal hydrochloric acid is run intothe filtered nitrite-free diazonium salt solution, whilst stirring. Ascoupling proceeds, the reaction mixture becomes viscous; it is thereforediluted with about 1,000 parts of water. After completion of coupling,the dye is filtered off and washed neutral with water. The paste of themonoazo dye is stirred into a mixture of 600 parts of acetic acid and 12parts of concentrated hydrochloric acid at from 50° to 60° C. Thetemperature is then lowered to 20°-25° C. by external cooling and asolution of 9.0 parts of sodium nitrite is added over from 5 to 10minutes. After about 60 minutes, the excess nitrite is removed withamidosulfonic acid. A solution of 25.6 parts of4-phenyl-2-(N-diallylamino)-thiazole in 40 parts of acetic acid is addedto the filtered diazonium salt solution over 30 minutes. The pH is thenraised to 2.5 with aqueous sodium acetate solution. After completion ofcoupling, the disazo dye is filtered off, washed first with isopropanoland then with hot water, and dried. The dye which has the followingformula ##STR13## is very suitable for printing cotton orcotton/polyester union fabrics. Navy to black dyeings are obtained.

The dyes summarized in the Table which follows can be prepared by amethod similar to that described in Example 1 and give dyeings havingsimilar properties.

    __________________________________________________________________________     ##STR14##                                                                    Ex-                                                                           ample                                                                             D        X.sup.1                                                                           Y.sup.1                                                                           B          B.sup.1 B.sup.2 Hue                           __________________________________________________________________________         ##STR15##                                                                             OCH.sub.3                                                                         OCH.sub.3                                                                          ##STR16## CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                   navy                          3   "        "   "                                                                                  ##STR17## "       "       "                             4   "        "   "                                                                                  ##STR18## "       "       "                             5   "        "   "   C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       "                             6   "        "   "                                                                                  ##STR19## CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                   "                             7                                                                                  ##STR20##                                                                             "   "                                                                                  ##STR21## "       "       "                             8   "        "   "                                                                                  ##STR22## "       "       "                             9   "        "   "                                                                                  ##STR23## "       "       "                             10  "        "   "                                                                                  ##STR24## "       "       "                             11                                                                                 ##STR25##                                                                             "   "   C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       "                             12  "        "   "                                                                                  ##STR26## CH.sub.3                                                                              CH.sub.3                                                                              "                             13                                                                                 ##STR27##                                                                             "   "   C.sub.6 H.sub.5                                                                          CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                   reddish blue                  14  "        "   "                                                                                  ##STR28## "       "       reddish blue                  15  "        "   "   "          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       reddish blue                  16  "        "   "                                                                                  ##STR29## CH.sub.3                                                                              CH.sub.3                                                                              reddish blue                  17  "        "   "                                                                                  ##STR30## "       "       reddish blue                  18                                                                                 ##STR31##                                                                             "   "   C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       violet                        19                                                                                 ##STR32##                                                                             CH.sub.3                                                                          CH.sub.3                                                                           ##STR33## CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                   "                             20                                                                                 ##STR34##                                                                             OCH.sub.3                                                                         OCH.sub.3                                                                          ##STR35## "       "       "                             21  "        "   "                                                                                  ##STR36## C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       "                             22  "        "   "                                                                                  ##STR37## "       "       "                             __________________________________________________________________________

EXAMPLE 23

20.7 parts of 2,6-dichloro-4-nitroaniline are introduced into a mixtureof 40 parts of concentrated sulfuric acid and 30 parts ofnitrosylsulfuric acid (of from 40 to 45% strength) at 10°-15° C., whilststirring, and the diazotization is allowed to take place overnight atroom temperature. The solution is then poured onto a mixture of 200parts of ice and 200 parts of water. After having removed excessnitrite, a solution of 15.3 parts of 1-amino-2,5-dimethoxybenzene in 300parts of water and 25 parts of 5-normal hydrochloric acid is added overabout 30 minutes. As coupling proceeds, the reaction mixture becomesviscous; it is therefore diluted with about 700 parts of water. Aftercompletion of coupling, the dye is filtered off and washed neutral withwater. The filter cake of the monoazo dye is dissolved in 400 parts ofacetic acid by stirring at room temperature and after adding 12 parts ofconcentrated hydrochloric acid the dye is diazotized with an aqueoussolution of 8.0 parts of sodium nitrite. After about 3 hours at 20°-25°C. the diazotization is complete, and a solution of 25.6 parts of4-phenyl-2-(N-diallylamino)-thiazole in 40 parts of acetic acid is addedto the nitrite-free diazonium salt solution. Coupling is then completedby means of an aqueous solution of 10 parts of sodium acetate, at pH3-4. The dye is filtered off and washed first with isopropanol and thenwith hot water. After drying under reduced pressure at 60° C., 46 partsof a dark powder having the following formula ##STR38## are obtained.This product is very suitable for printing cotton or cotton/polyesterunion fabrics. Navy to black dyeings are obtained.

The dyes summarized in the Table which follows can be prepared by amethod similar to that described in Example 23 and give dyeings havingsimilar properties.

    __________________________________________________________________________     ##STR39##                                                                    Ex-                                                                           ample                                                                             D               X.sup.1                                                                           Y.sup.1                                                                           B          B.sup.1 B.sup.2     Hue                __________________________________________________________________________    24                                                                                 ##STR40##      OCH.sub.3                                                                         OCH.sub.3                                                                         C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           black              25  "               "   "   "          "       C.sub.6 H.sub.5                                                                           "                  26  "               "   "                                                                                  ##STR41## CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                       "                  27                                                                                 ##STR42##      "   "   C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 COOC.sub.2                                                    H.sub.5     "                  28                                                                                 ##STR43##      "   "                                                                                  ##STR44## CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                       "                  29  "               "   "                                                                                  ##STR45## "       "           "                  30                                                                                 ##STR46##      "   CH.sub.3                                                                          C.sub.6 H.sub.5                                                                          "       "           navy               31  "               "   "   "          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           "                  32  "               "   "   "          "       C.sub.2 H.sub.4 COOC.sub.2                                                    H.sub.5     "                  33  "               "   "                                                                                  ##STR47## CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                       "                  34  "               "   OCH.sub.3                                                                         C.sub.6 H.sub.5                                                                          C.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 OH                                                                        "                  35  "               "   "                                                                                  ##STR48## C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           black              36  "               "   CH.sub.3                                                                           ##STR49## C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OCOOC.sub.2                                                    H.sub.5    "                  37  "               "   "                                                                                  ##STR50## CH.sub.3                                                                              CH.sub.3    "                  38  "               "   "                                                                                  ##STR51## CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                       navy               39  "               "   "                                                                                  ##STR52## "       "           violet             40                                                                                 ##STR53##      CH.sub.3                                                                          CH.sub.3                                                                           ##STR54## "       "           black              41                                                                                 ##STR55##      OCH.sub.3                                                                         OCH.sub.3                                                                         C.sub.6 H.sub.5                                                                          "       "           "                  42  "               "   "   "          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           "                  43  "               "   "   "          "       C.sub.2 H.sub.4 COOCH.sub.3                                                   .           "                  44                                                                                 ##STR56##      "   "   "          "       C.sub.2 H.sub.5                                                                           "                  45                                                                                 ##STR57##      "   "   "          CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                       blue               46  "               "   "   "          "       "           "                  47  "               "   "                                                                                  ##STR58## "       "           "                  48                                                                                 ##STR59##      CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           "                  49                                                                                 ##STR60##      "   "   "          "       "           "                  50                                                                                 ##STR61##      OCH.sub.3                                                                         OCH.sub.3                                                                         "          "       "           violet             51  "               "   "   "          "       C.sub.2 H.sub.4 CN                                                                        "                  52  "               "   "   "          "       C.sub.2 H.sub.4 OCOCH.sub.3                                                               "                  53                                                                                 ##STR62##      "   "   "          C.sub.2 H.sub.4 OCOCH.sub.3                                                           "           navy               54                                                                                 ##STR63##      "   CH.sub.3                                                                           ##STR64## C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 COOC.sub.2                                                    H.sub.5     blue               55                                                                                 ##STR65##      "   "                                                                                  ##STR66## "       C.sub.2 H.sub.5                                                                           "                  56                                                                                 ##STR67##      "   "   "          "       "           "                  57                                                                                 ##STR68##      "   "   "          "       "           "                  58                                                                                 ##STR69##      "   "   "          "       "           "                  59                                                                                 ##STR70##      "   OCH.sub.3                                                                         C.sub.6 H.sub.5                                                                          CH.sub.2 CHCH.sub.2                                                                   C.sub.2 H.sub.4 COOC.sub.2                                                    H.sub.5     black              60                                                                                 ##STR71##      "   CH.sub.3                                                                           ##STR72## C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.7                                                                           "                  61                                                                                 ##STR73##      "   OCH.sub.3                                                                         C.sub.6 H.sub.5                                                                          C.sub.4 H.sub.9                                                                       C.sub.4 H.sub.9                                                                           "                  62  "               "   CH.sub.3                                                                           ##STR74## "       "           "                  63  "               "   "                                                                                  ##STR75## C.sub.3 H.sub.7                                                                       C.sub.2 H.sub.4 COOOC.sub.2                                                    H.sub.5    "                  64  "               "   "   "          CH.sub.3                                                                               ##STR76##  "                  65                                                                                 ##STR77##      "   "                                                                                  ##STR78## C.sub.2 H.sub.5                                                                       "           blue               66                                                                                 ##STR79##      "   "   "          "       C.sub.2 H.sub.5                                                                           green- ish                                                                    blue               67  "               "   "                                                                                  ##STR80## CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                       green- ish                                                                    blue               68                                                                                 ##STR81##      "   "   C.sub.6 H.sub.5                                                                          "       "           blue               __________________________________________________________________________

EXAMPLE 69

13.8 parts of p-nitroaniline are diazotized in the conventional manner.A solution of 15 parts of α-naphthylamine in 50 parts of acetic acid isallowed to run into the filtered nitrite-free diazonium salt solution,whilst stirring. As coupling proceeds, the reaction mixture becomesviscous. It is therefore diluted with about 400 parts of water. Aftercompletion of coupling, the pH is brought to 6-7 with 30% strengthaqueous sodium hydroxide solution. The dye is filtered off and washedthoroughly with water. The paste of the monoazo dye is stirredthoroughly into a mixture of 800 parts of acetic acid and 12 parts ofconcentrated hydrochloric acid at 50°-60° C. The temperature is thenlowered to 0°-10° C. by external cooling and a solution of 8.3 parts ofsodium nitrite is added over 5-10 minutes. After about 30 minutes, theexcess nitrite is removed with amidosulfonic acid. A solution of 26.6parts of 2-(n-β-methoxycarbonylethyl-N-ethyl)-4-phenylthiazole in 60parts of acetic acid is added to the filtered diazonium salt solutionover 30 minutes. The pH is then raised to 2.5 with aqueous sodiumacetate solution. After completion of coupling, the disazo dye isfiltered off, washed first with isopropanol and then with hot water, anddried. The dye, which has the following structure ##STR82## is verysuitable for dyeing or printing cotton or cotton/polyester unionfabrics. Navy to black dyeings are obtained.

The dyes summarized in the Table which follows can be prepared by amethod similar to that described in Example 1 and give dyeings havingsimilar properties.

    ______________________________________                                         ##STR83##                                                                    Ex-                                                                           ample R              R.sup.1     R.sup.2                                      ______________________________________                                        70    C.sub.6 H.sub.5                                                                              CH.sub.3                                                                                   ##STR84##                                   71    "              C.sub.2 H.sub.4 OH                                                                        CH.sub.3                                     72    "              "           C.sub.2 H.sub.5                              73    "              CH.sub.3                                                                                   ##STR85##                                   74    "              C.sub.2 H.sub.5                                                                           "                                            75    "              CH.sub.2 CHCH.sub.2                                                                       CH.sub.2 CHCH.sub.2                          76    "                                                                                             ##STR86##                                                                                 ##STR87##                                   77    "              C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                              78    "              "           C.sub.2 H.sub.4 CN                           79    "              CH.sub.3    C.sub.6 H.sub.5                              80    "                                                                                             ##STR88##                                               81    "                                                                                             ##STR89##                                               82    "                                                                                             ##STR90##                                               83                                                                                   ##STR91##     CH.sub.2 CHCH.sub.2                                                                       CH.sub.2 CHCH.sub.2                          84                                                                                   ##STR92##     C.sub.3 H.sub.7                                                                           C.sub.3 H.sub.7                              85                                                                                   ##STR93##     CH.sub.2 CHCH.sub.2                                                                       CH.sub.2 CHCH.sub.2                          86                                                                                   ##STR94##     "           "                                            87    "              C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                              88    "              "                                                                                          ##STR95##                                   89    "              C.sub.3 H.sub.7                                                                           C.sub.3 H.sub.7                              90                                                                                   ##STR96##     CH.sub.2 CHCH.sub.2                                                                       C.sub. 2 H.sub.4 COCH.sub.3                  91                                                                                   ##STR97##     C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                              92                                                                                   ##STR98##     "                                                                                          ##STR99##                                   93                                                                                   ##STR100##    H                                                                                          ##STR101##                                  94                                                                                   ##STR102##    C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 CN                           95    H              "           C.sub.2 H.sub.5                              96    CH.sub.3       "                                                                                          ##STR103##                                  97    "              CH.sub.2 CHCH.sub.2                                                                       "                                            98                                                                                   ##STR104##    C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                              99                                                                                   ##STR105##    "           "                                            100                                                                                  ##STR106##    CH.sub.2 CHCH.sub.2                                                                       CH.sub.2 CHCH.sub.2                          101   HO             "           C.sub.2 H.sub.5                              ______________________________________                                    

    __________________________________________________________________________     ##STR107##                                                                   Example                                                                            D           R          R.sup.1 R.sup.2                                   __________________________________________________________________________    102                                                                                 ##STR108## C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                        ##STR109##                               103  "                                                                                          ##STR110##                                                                              "       "                                         104  "                                                                                          ##STR111##                                                                              "       "                                         105                                                                                 ##STR112##                                                                                ##STR113##                                                                              "       C.sub.2 H.sub.5                           106  C.sub.6 H.sub.5                                                                           "          CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                       107                                                                                 ##STR114## C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4OCOCH.sub.3                108                                                                                 ##STR115## "          "       "                                         109  "           "          "       C.sub.2 H.sub.5                           110                                                                                 ##STR116## "          "       "                                         111                                                                                 ##STR117##                                                                                ##STR118##                                                                              CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                       112  "                                                                                          ##STR119##                                                                              C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                           113                                                                                 ##STR120##                                                                                ##STR121##                                                                              "       "                                         114  "                                                                                          ##STR122##                                                                              "       "                                         115  "                                                                                          ##STR123##                                                                              CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                       116                                                                                 ##STR124## C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                           117                                                                                 ##STR125##                                                                                ##STR126##                                                                              CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                       118                                                                                 ##STR127## C.sub.6 H.sub.5                                                                          CH.sub.2 CHCH.sub.2                                                                    ##STR128##                               119  "                                                                                          ##STR129##                                                                              C.sub.2 H.sub.5                                                                       "                                         120  "           C.sub.6 H.sub.5                                                                          "       C.sub.2 H.sub.4 CN                        121                                                                                 ##STR130## "          "                                                                                      ##STR131##                               122                                                                                 ##STR132## "          "                                                                                      ##STR133##                               123  "                                                                                          ##STR134##                                                                              "       "                                         125  "           C.sub.6 H.sub.5                                                                          CH.sub.2 CHCH.sub.2                                                                   "                                         126  "                                                                                          ##STR135##                                                                              C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                           127  "           C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                        ##STR136##                               128  "                                                                                          ##STR137##                                                                              "                                                                                      ##STR138##                               129                                                                                 ##STR139## C.sub.6 H.sub.5                                                                          "                                                                                      ##STR140##                               130                                                                                 ##STR141## C.sub.6 H.sub.5                                                                          CH.sub.2 CHCH.sub.2                                                                    ##STR142##                               131  "                                                                                          ##STR143##                                                                              "       "                                         132                                                                                 ##STR144##                                                                                ##STR145##                                                                              C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                           133                                                                                 ##STR146## C.sub.6 H.sub.5                                                                          CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                       134  "           "          C.sub.3 H.sub.7                                                                       C.sub.3 H.sub.7                           __________________________________________________________________________

EXAMPLE 135

18.3 parts of 2,4-dinitroaniline are introduced into a mixture of 29parts of nitrosylsulfuric acid (containing 13.1% of dinitrogen trioxide)and 120 parts of 85% strength sulfuric acid at 0°-5° C., whilststirring. After about 4 hours at 0°-5° C., the diazotization is completeand the solution is added dropwise, whilst stirring, to a solution of 15parts of α-naphthylamine, 400 ml of water and 15 parts of concentratedhydrochloric acid, which is cooled to 0° C. by adding 400 parts of ice.Coupling is complete after 2-3 hours. The reaction mixture isneutralized with dilute sodium hydroxide solution, the product isfiltered off and washed salt-free with water, and thereafter theprocedure is continued as in Example 69. The resulting disazo dye,having the following composition ##STR147## dyes cotton, andcotton/polyester union fabrics, in lightfast greenish blue hues.

The dyes summarized in the Table which follows can be prepared by amethod similar to that described in Example 135 and give dyeings havingsimilar properties.

    __________________________________________________________________________     ##STR148##                                                                   Example                                                                            D           R         R.sup.1 R.sup.2                                    __________________________________________________________________________    136                                                                                 ##STR149## C.sub.6 H.sub.5                                                                         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                            137  "           "                                                                                        ##STR150##                                                                            ##STR151##                                138  "           "         CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                        139  "                                                                                          ##STR152##                                                                             "       "                                          140  "                                                                                          ##STR153##                                                                             "       "                                          141  "                                                                                          ##STR154##                                                                             C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                            142  "           C.sub. 6 H.sub.5                                                                        "       C.sub.2 H.sub.4 CN                         143  "                                                                                          ##STR155##                                                                             "       "                                          144  "           H         "       C.sub.2 H.sub.5                            145  "           CH.sub.3  CH.sub.2 CHCH.sub.2                                                                    ##STR156##                                146  "                                                                                          ##STR157##                                                                             C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                            147  "                                                                                          ##STR158##                                                                             "       "                                          148  "                                                                                          ##STR159##                                                                             "       "                                          149  "           HO        "       "                                          150  "           CH.sub.3  H                                                                                      ##STR160##                                151                                                                                 ##STR161## C.sub.6 H.sub.5                                                                         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                            152  "                                                                                          ##STR162##                                                                             "       "                                          153                                                                                 ##STR163## C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.5                                                                       "                                          154  "           "         CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                        155                                                                                 ##STR164## "         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                            156                                                                                 ##STR165## "         "       "                                          157                                                                                 ##STR166## "         C.sub.2 H.sub.5                                                                        ##STR167##                                158  "           "         "       C.sub.2 H.sub.5                            159                                                                                 ##STR168##                                                                                ##STR169##                                                                             "       "                                          160  "           "         "                                                                                      ##STR170##                                161                                                                                 ##STR171## C.sub.6 H.sub.5                                                                         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                            162                                                                                 ##STR172## "         "       "                                          163                                                                                 ##STR173## "         "       "                                          164                                                                                 ##STR174## "         "       "                                          165  "                                                                                          ##STR175##                                                                             "       "                                          166  "                                                                                          ##STR176##                                                                             C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 CN                         167  "                                                                                          ##STR177##                                                                             "       C.sub.2 H.sub.5                            168  "           CH.sub.3  CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                        169  "           C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                    170                                                                                 ##STR178## "         "       "                                          171                                                                                 ##STR179## "         CH.sub.2 CHCH.sub.2                                                                    ##STR180##                                172                                                                                 ##STR181##                                                                                ##STR182##                                                                             "       "                                          173                                                                                 ##STR183## "         "       "                                          174                                                                                 ##STR184## C.sub.6 H.sub.5                                                                         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                            175                                                                                 ##STR185## "         "       "                                          176                                                                                 ##STR186## "         "       "                                          177                                                                                 ##STR187## "         "                                                                                      ##STR188##                                178                                                                                 ##STR189## "         C.sub.3 H.sub.7                                                                       "                                          179                                                                                 ##STR190## "         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                            180                                                                                 ##STR191##                                                                                ##STR192##                                                                             "       "                                          181                                                                                 ##STR193## "         "                                                                                      ##STR194##                                182                                                                                 ##STR195## C.sub.6 H.sub.5                                                                         "       "                                          183                                                                                 ##STR196## "         "                                                                                      ##STR197##                                184  "           "         CH.sub.2 CHCH.sub.2                                                                   "                                          185  "           "         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                            186                                                                                 ##STR198## "         "       "                                          187                                                                                 ##STR199## "         CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                        188                                                                                 ##STR200## "         "       "                                          189                                                                                 ##STR201## "         "       "                                          190                                                                                 ##STR202##           "       "                                          __________________________________________________________________________

We claim:
 1. A compound of the formula: ##STR203##
 2. A compound of theformula: ##STR204##